32 - Carbonates Fluid Formulations

Carbonate Acidizing
CarboSTIM
Acid Formulations
Copyright 2009, NExT, All rights reserved

Acid formulations
HCl - Primary acid for Emulsified acids

carbonates • HCl / organic blends
Organic acids: Viscosified acids
• Less dissolution capacity • Self diverting acids
• Higher temperatures
• VES acid system
Intensified Acid
Non Acid Reactive Systems
Gas well acid
• EDTA & HEDTA
Acid dispersion
• Spearhead to prevent organic
deposit
2
CO2 m3/m3
Acid Density kg/m3 of CaCO3 Used acid
(15,6°C) density (SCF/BBL)
disolved
HCl 7,5 % 1,037 106 1,1 24 (134)

HCl 15 % 1,0749 222 1,17 50 (278)
HCl 20 % 1,10 300 1,23 68 (379)
HCl 28 % 1,147 437 1,34 98 (550)
Acetic 10 % 1,0125 88* 1,08 20 (111)
Acetic 12 % 1,0154 101* 1,08 23 (127)
Formic 9 % 1,02 98 1,08 22 (123)
3
HCl formulation preparation
Dilution of HCl concentrate

• 33% solution
• Clean tank to avoid iron contamination
• Dilution with water heat generation
Always add acid in water
Additives addition
• Corrosion inhibitor, etc
• Add separately additives, one by one in a vortex area and mixe
• Roll the tank for at least 20 minutes after all additions
Rules valid for all acids and formulations
4
REACTION PRODUCTS AND PROPERTIES OF HYDROCHOLORIC ACID
(Numbers based on 1000 gallons of acid or
the reaction of 1000 gallons of acid)
Hydrochloric Acid 7.5% 15% 20% 25% 28%
Density acid in lbs/gal 8.644 8.961 9.169 9.385 9.521
Specific gravity of acid 1.037 1.075 1.100 1.126 1.142
Gallons of water in acid 959 914 879 845 822
Lbs of CaCO3 dissolved (as calcite) 888 1843 2512 3213 3652
Cu ft of CaCO3 dissolved 5.25 10.9 14.9 19.0 21.6
Lbs of dolomite dissolved 824 1700 23115 2960 3267
Cu ft of dolomite dissolved 4.6 9.5 12.93 16.56 18.8
Lbs of CO2 formed 391 811 1105 1414 1607
Gallons of H2O formed 19.2 39.7 54.2 69.5 78.8
Approx. gallons of spent acid water 1011 1020 1025 1032 1035
Viscosity of acid (water = 1) 1.14 1.33 1.59 1.7 1.87
Viscosity of spent acid (water = 1) 1.35 1.94 2.69 3.40 3.90
Specific gravity of spent acid 1.096 1.175 1.233 1.295 1.34
Density of spent acid in lbs/gal 9.14 9.79 10.28 10.79 11.17
Concentration of spent acid as calcium chloride 11% 20% 26% 32% 36%
5
Organic Acids
Three formulations used in the field for carbonates

• Aqueous acetic acid
• Nonaqueous acetic acid
• Formic acid
6
Organic Acids
10000
1000
100
15% HCl
9% Formic
10% Acetic
10
0.1
(ft3) (lbm) Cx
Volume of CO2 Limestone Relative Reaction
Dissolved Rate
7
Aqueous Acetic Acid
Advantages
• Can be inhibited for use at high temperature and extended
exposure time
• Slow reaction rate with carbonates
• Effective control of ferric irons at less than 50°C - 125o F.
• Complexes Aluminum
8
Aqueous Acetic Acid
Concentration
• 10% of glacial acetic acid in water
• freezing point = 62o F
• (70% acetic acid) - freezing point = -3o F
• can be used when freezing is a problem
• Specific Inhibitor
9
Non aqueous Acetic Acid
Glacial acetic acid in kerosene or diesel

• Advantages
• Effective in removing water block
• Water sensitive formations
• Deep penetration
Glacial acetic acid in kerosene or diesel
• Inhibition
• Non corrosive until contacting water
• Specific inhibitor is recommended
10
Formic Acid
Concentration - up to 9%
Slow reaction with carbonates
Intermediate between HCl and Acetic Acid
Inhibited for use up to 350o F
Also used as preflush to organic mud acid
Compatible with mutual solvents and most other additives
used with HCl
Limitations
• Concentration below 9%
Precipitation of calcium formate if concentration is above 9%
11
Intensified Acid
15% HCl and 0.25% HF

Used in dolomitic limestone
Beware of CaF2
12
Acid Dispersion
Primary use is for removal of Hydrocarbon

commingled hydrocarbon and scale
deposits
• Paraffin
• Calcite
Minimize acid-oil incompatibility
problems
Dissolve carbonates
Some viscosity (diversion) Acid
13
Acid Dispersion
• Blend aromatic solvent with any acid blend

• HCl
• Mud Acid
• Organic acid
• Blended Acids
Dispersing agent
Use corrosion inhibitors that are appropriate for the acid
system
Specific blending procedure using two tanks and a choke
14
Gas well Acid
• Acid + 67% Methanol (by volume)

• Slow reaction rate
• Lowers surface tension
• Increases vapor pressure
• Improves spent acid clean up
• Acid Retardation
Applications
• Dry gas wells and gas storage wells
• Temperature up to 250o F
15
Gas Well Acid Surface Tension
Surface Tension DYNE/CM
Temp = 77 F
Volume Percent of Alcohol in Solution
16
CarboSTIM
Viscosified Acid

Acid Systems: Interaction with Rock
Regular HCl SGD
Emulsified HCl
VES-HCl
SPE 71693 SPE 80225

18
Acid Emulsions
Problem:
Hydrochloric acid (HCl) does not penetrate
(wormhole) more than a few inches into the
formation in high temperature wells.
Benefits:
• Improved damage bypass via deeper
wormhole penetration in high temperature
wells
• Deeper live acid penetration.
• Superior corrosion inhibition due to the oil
outside phase
19
Acid emulsion
Hydrocarbon
Hydrocarbon external emulsion
• 15% to 30% hydrocarbon
Acid
• Up to 28% HCl
• Stable emulsions can be formulated for
~350F
Effective diffusivity ~400 times lower than HCl
[Li, et. al., 1993].
Leak-off control is achieved by emulsion and
by reduced effective reaction rate.
20
HCl and Emulsion
HCl field concentrations are between 7.5 wt% and 36 wt%

16000 35
Volume of CO2 (ft3)
14000 Limestone Dissolved (lbm)
Limestone Dissolved (ft3)
30
12000
25
10000
20
8000
15
6000
10
4000
2000 5
0 0
0 5 10 15 20 25 30
HCl Concentration (wt %)
21
Emulsion Reaction Retardation
Emulsion is significantly retarded with respect to HCl

20
28%
19 20%
15%
Retardation Factor
18
17
16
15
14
250 300 350
Temperature [ oF]
(Navarrete et al., SPE50612, 1998)
22
Emulsion Stability
Emulsion is stable for approximately one hour at 350oF.

Emulsion stability improves corrosion inhibition.
Stability of Emulsion at Bottomhole
Static Temperatures
Temperature Required Time for 50%

° F [ ° C] Emulsion Break
250 [121] >12 hr
275 [135] 6 hr
300 [149] 4 hr
325 [163] > 2 hr
350 [177] ~1 hr
23
Conclusions
Acid emulsion is a highly retarded emulsified HCl acid

system used for:
• Improved damage bypass via deeper wormhole penetration in
high temperature wells
• Deeper live acid penetration
• Behaves as a viscosified acid and add a diversion mechanism
Applications
• High temperature matrix stimulation of carbonate formations
i.e. temperature range 250oF-350oF
• Acid fracturing of high temperature carbonate reservoirs.
24
Gelled acid for diversion
It is possible to viscosify HCl solutions using :

Specific polymers called Self Gelling Diverters : SGD
• They break with the PH
Viscous Elastic Surfactant : VES
• They break with the oil produced during flow back
25
Self-gelling diverter
Low viscosity if pH < 2

µ = 20 cp µ
Crosslinks when pH = 3
µ = 1000 cp
Rigid crosslinked gel
Breaks back when pH = 4
µ = 15 cp pH
2 4
26
Self-gelling diverter
Live Acid Spent acid gel

µ
pH
2 4
27
Self Diverting Acid
Self-selective treatment
No damaging, solid particles in the fluid system :
flowed back from the well along with the spent acid
Applications :
• First applications in carbonates
• Used also in sandstone but with mixed results
Best formulation :
low acid strength in SGD stage
high acid strength in neat acid stage
28
VES in HCl Solutions
CaCO3 + 2HCl ---> CaCl2 + CO2 + H2O
spent
acid
Worm-like Micelle
Monomers
29
VES: Molecular Structure
• Amino Acid-type Species

• Amphoteric
• Long Hydrocarbon Tail
• Size = 1/2000 Guar Molecule
30
VES acid
• Viscoelastic Surfactant-based Leakoff Control Acid

• Polymer-Free
• Solutions of the Same Surfactant & HCl
• Low Viscosity System
• Control Leak-off Effectively
• No Metal Cross-linker (Eliminates Hydroxide and
Sulfide Precipitation) a
• Gel Breaking is Controlled
a (Nasr-El-Din et al., SPE 75257, 2002)
31
VES Structure in KCl Solutions
10 µm
Cryo Electron Microscope Image of VES Fluid

32
VES in KCl Solutions
T Apparent Viscosity (cp) at

F 40 s -1 100 s -1 170 s -1 511 s -1
80 206 137 108 67
125 232 131 95 48
150 212 133 101 58
175 224 136 102 56
200 206 186 95 51
5 vol% VES + 4 wt% KCl brine; Fann 50 Rheometer
33
VES-HCl: Gelling & Breaking
Live VES Acid + Spent Acid + Mutual Solvent
34
Viscosity of Live VES-HCl Solutions
250
200
Viscosity @170 s-1
150
100
Used in the Treatment

50
0
0 5 10 15 20 25 30
HCl Concentration (%)
7 vol% VES; Fann 35 @ RT

35
Viscosity of Spent VES-HCl
o
Apparent Viscosity (cp) at
T ( F) -1 -1 -1
40 s 100 s 170 s
70 520 339 264
100 490 320 250
125 613 312 210
150 826 396 258
175 381 204 142
200 462 189 112
225 480 204 124
250 345 216 165
275 190 135 110
300 127 68 47
7 vol% VES, 20 wt% HCl; Fann 50

36
VES Fluids: Complete Break
Worm-like Micelle
Mutual Solvent
Breaking
• Contact with hydrocarbons
• Dilution with injection water Spherical Micelles
37
Comparison Emulsified acid and Gelled acid
Emulsified acid creates longer wormholes

In situ gelled acid creates shallow wormholes
Obviously, a stage-wise treatment that utilizes both acids can achieve
deep, and wider wormholes.
It is also recommended to increase the concentration of iron control
chemicals in the in-situ acids. This is to account for iron present in the
formation and iron that is produced by corrosion.
Finally, in-situ gelled and emulsified acids are retarded acids. It is
therefore recommended to increase the soaking time in the formation
to ensure complete spending of these acids.
SPE 65386: Jack D. Lynn, Saudi Aramco, H. A. Nasr-El-Din, Saudi Aramco
38
Non Acid Reactive Solution using EDTA
Used as formation clean up or
breakdown fluid in formations
Ca++
that may be damaged by acid
Contain strong chelating and
clay suspending agents Dissolution of Calcium Carbonate by EDTA
Applicable > 200°C - 400oF Low pH

H+ + CaCO3 Ca+2 + HCO3-
Ca+2 + H2Y-2 CaY-2 + 2H+
Not recommended below 35°C (pH=4) H2Y-2 + CaCO3 CaY-2 + CO2 + H2O
- 100o F
High pH
May be shut in or immediately (pH=8.8) HY-3 + CaCO3 CaY-2 + HCO3-

Y-4 + CaCO3 CaY-2 + CO3-2
returned (pH > 12)
39
EDTA applications
EDTA or HEDTA can be formulated to match temperature

and reactivity
Low corrosion rate
Prevent problem associated with mobile silica
Candidates:
• Gas wells
• Acid sensitive formations
• High temperature wells
40

32 - Carbonates Fluid Formulations

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

32 - Carbonates Fluid Formulations

Uploaded by

Copyright:

Available Formats

Carbonate Acidizing

Copyright 2009, NExT, All rights reserved

HCl - Primary acid for Emulsified acids

HCl 7,5 % 1,037 106 1,1 24 (134)

Dilution of HCl concentrate

Three formulations used in the field for carbonates

• Slow reaction rate with carbonates

• Effective control of ferric irons at less than 50°C - 125o F.

Glacial acetic acid in kerosene or diesel

15% HCl and 0.25% HF

Primary use is for removal of Hydrocarbon

• Blend aromatic solvent with any acid blend

• Acid + 67% Methanol (by volume)

Volume Percent of Alcohol in Solution

Copyright 2009, NExT, All rights reserved

Regular HCl SGD

SPE 71693 SPE 80225

HCl field concentrations are between 7.5 wt% and 36 wt%

Emulsion is significantly retarded with respect to HCl

Emulsion is stable for approximately one hour at 350oF.

Temperature Required Time for 50%

Acid emulsion is a highly retarded emulsified HCl acid

It is possible to viscosify HCl solutions using :

Low viscosity if pH < 2

Live Acid Spent acid gel

CaCO3 + 2HCl ---> CaCl2 + CO2 + H2O

• Amino Acid-type Species

• Viscoelastic Surfactant-based Leakoff Control Acid

a (Nasr-El-Din et al., SPE 75257, 2002)

Cryo Electron Microscope Image of VES Fluid

T Apparent Viscosity (cp) at

5 vol% VES + 4 wt% KCl brine; Fann 50 Rheometer

Live VES Acid + Spent Acid + Mutual Solvent

Used in the Treatment

HCl Concentration (%)

7 vol% VES; Fann 35 @ RT

7 vol% VES, 20 wt% HCl; Fann 50

Emulsified acid creates longer wormholes

Applicable > 200°C - 400oF Low pH

May be shut in or immediately (pH=8.8) HY-3 + CaCO3 CaY-2 + HCO3-

EDTA or HEDTA can be formulated to match temperature

You might also like